KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling

KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC02012G, Paper

Prashant Gautam, Mahak Dhiman, Vivek Polshettiwar, Bhalchandra M. Bhanage
This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki-Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1) with very high turnover number.

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC02012G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki–Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1). Under mild reaction conditions, the KCC-1-PEI/Pd catalytic system showed a turnover number (TON) 28-times and a turnover frequency (TOF) 51-times higher than the best supported Pd catalyst reported in the literature for the carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid, as a test reaction. Also, the catalyst could be recycled up to ten times with a marginal loss in activity after the eighth cycle. The high activity of the catalyst can be attributed to the fibrous nature of the KCC-1 support and PEI functionalization provided the enhanced stability.

(4-methoxyphenyl)(phenyl)methanone (3b) 59.3 mg, yield 56%

1H NMR (500 MHz, CDCl3): δ 7.86 (d, J = 8.6 Hz, 2H), 7.78 (d, J = 7.6 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 6.99 (d, J = 8.6 Hz, 2H), 3.92 (s, 3H).

13C{1H}NMR (125 MHz, CDCl3): δ 195.4, 163.1, 138.2, 132.4, 131.8, 130.0, 129.6, 128.1, 113.4, 55.4.

GCMS (EI, 70 eV): m/z (%): 212 (40), 135 (100), 105 (14), 77 (36).

KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki–Miyaura cross-coupling

Prashant Gautam,^a   Mahak Dhiman,^b   Vivek Polshettiwar*^b and  Bhalchandra M. Bhanage*^a  

*Corresponding authors

^aDepartment of Chemistry, Institute of Chemical Technology, N.P. Marg, Matunga-400019, Mumbai, India
E-mail: bm.bhanage@ictmumbai.edu.in,bm.bhanage@gmail.com

^bNanocatalysis Laboratories (NanoCat), Department of Chemical Sciences, Tata Institute of Fundamental Research (TIFR), Homi Bhabha Road, Colaba, Mumbai, India
E-mail: vivekpol@tifr.res.in

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02012G

Prashant Gautam

Bhalchandra M. Bhanage

\\\\\\\\\\KCC-1 supported,  palladium nanoparticles, sustainable nanocatalyst, carbonylative Suzuki-Miyaura cross-coupling, Prashant Gautam, Mahak Dhiman, Vivek Polshettiwar, Bhalchandra M. Bhanage

Multicomponent-Multicatalyst Reactions (MC)2R: Efficient Dibenzazepine Synthesis

Multicomponent-Multicatalyst Reactions (MC)2R: Efficient Dibenzazepine SynthesisJennifer Tsoung, Jane Panteleev, Matthias Tesch, and Mark Lautens

Org. Lett. 2014, 16, 110-113. DOI:10.1021/ol4030925 .

http://pubs.acs.org/doi/abs/10.1021/ol4030925

A Rh^I/Pd⁰ catalyst system was applied to the multicomponent synthesis of aza-dibenzazepines from vinylpyridines, arylboronic acids, and amines in a domino process with no intermediate isolation or purification.

5-(p-tolyl)-3-(trifluoromethyl)-10,11-dihydro-5H-benzo[b]pyrido[2,3-f]azepine (4a)

1H NMR
(400 MHz, CDCl3) δ 8.66 (d, J = 1.1 Hz, 1H), 7.97 (d, J = 1.8 Hz, 1H), 7.43 – 7.38 (m, 1H), 7.38 – 7.29
(m, 3H), 6.98 (d, J = 8.4 Hz, 2H), 6.57 – 6.51 (m, 2H), 3.33 – 3.21 (m, 2H), 3.09 – 2.99 (m, 2H), 2.26 (s,
3H);

13C NMR (101 MHz, CDCl3) δ 161.7 (q, J = 1.3 Hz), 145.8, 143.6, 143.4 (q, J = 4.0 Hz), 139.7,
139.5, 134.9 (q, J = 3.5 Hz), 130.3, 130.0, 129.9, 128.9, 128.2, 127.7, 125.3 (q, J = 33.1 Hz), 123.4 (q, J =
272.5 Hz), 114.0 (2), 35.9, 29.0, 20.4;

19F NMR (377 MHz, CDCl3) δ -62.0;

IR (NaCl, neat): 3063, 3028,
2926, 2862, 1616, 1506, 1489, 1456, 1435, 1429, 1410, 1339, 1319, 1296, 1267, 1240, 1207, 1165, 1128,
1086, 1036, 978, 947, 930, 910, 895, 808, 772, 756, 737, 721, 704, 687, 664, 646, 627 cm-1;

HRMS (ESI):
calcd for C21H18F3N2 (M+H)+: 355.1422; found. 355.1419.

Jennifer Tsoung

Jennifer Tsoung

PhD graduate, organic chemistry

Experience

PhD

University of Toronto

September 2010 – October 2015 (5 years 2 months)

Research Intern

Kyoto University

June 2014 – August 2014 (3 months)Kyoto, Japan

Methodology project in asymmetric phase-transfer catalyzed alkylations.

Co-op student

Angiotech

May 2009 – August 2009 (4 months)Vancouver, Canada Area

Formulation chemistry

Co-op student

Boehringer Ingelheim

January 2008 – August 2008 (8 months)Montreal, Canada Area

On two hit-to-lead teams working to synthesize analogues of hit compounds for HIV research.

Publications

Diastereoselective Friedel−Crafts Alkylation of Hydronaphthalenes(Link)

The Journal of Organic Chemistry

September 27, 2011

An efficient and versatile synthesis of chiral tetralins has been developed using both inter- and intramolecular Friedel-Crafts alkylation as a key step. The readily available hydronaphthalene substrates were prepared via a highly enantioselective metal-catalyzed ring opening of meso-oxabicyclic alkenes followed by hydrogenation. A wide variety of complex tetracyclic compounds have been isolated...more

One-Pot Synthesis of Chiral Dihydrobenzofuran Framework via Rh/Pd Catlaysis

Organic Letters

October 12, 2012

A one-pot synthesis of the chiral dihydrobenzofuran framework is described. The method utilizes Rh-catalyzed asymmetric ring opening (ARO) and Pd-catalyzed C-O coupling to furnish the product in excellent enantioselectivity without isolation of intermediates. Systematic metal-ligand studies were carried out to investigate the compatibility of each catalytic system using product enantiopurity as an...more

Rh/Pd Catalysis with Chiral and Achiral Ligands: Domino Synthesis of Aza-Dihydrodibenzoxepines(Link)

Angew. Chem. Int. Ed

July 19, 2013

A game of dominoes: A synthetic route to aza-dihydrodibenzoxepines is described, through the combination of a Rh-catalyzed arylation and a Pd-catalyzed C-O coupling in a single pot. For the first time, the ability to incorporate a chiral and an achiral ligand in a two-component, two-metal transformation is achieved, giving the products in moderate to good yields, with excellent enantioselectivities.

Multicomponent-multicatalyst reactions (MC)(2)R: efficient dibenzazepine synthesis.

Organic Letters

January 13, 2014

A Rh(I)/Pd(0) catalyst system was applied to the multicomponent synthesis of aza-dibenzazepines from vinylpyridines, arylboronic acids, and amines in a domino process with no intermediate isolation or purification.

Formation of substituted oxa- and azarhodacyclobutanes.

Chemistry - A European Journal

December 6, 2013

The preparation of substituted oxa- and azarhodacyclobutanes is reported. After exchange of ethylene with a variety of unsymmetrically and symmetrically substituted alkenes, the corresponding rhodium-olefin complexes were oxidized with H2O2 and PhINTs (Ts=p-toluenesulfonyl) to yield the substituted oxa- and azarhodacyclobutanes, respectively. Oxarhodacyclobutanes could be prepared with excellent...more

Education

University of Toronto

Doctor of Philosophy (PhD), Organic Chemistry

2010 – 2014

Activities and Societies: Pueblo Science executive member, Let's Talk Science volunteer, International Chemistry Olympiad tutor

The University of British Columbia

Bachelor of Science (BSc), Chemistry

2005 – 2010

Activities and Societies: Undergraduate Chemistry Society (UCS) executive member, Science Undergraduate Society (SUS) executive member, Science Co-op Students Association (SCOOPS) president and founding member

port moody secondary

High school

Mark Nitz presents Jennifer Tsoung certificate for her CTFP award

Women in Chemistry group, 2015

Lautens Research Group :: Group Pictures

www.chem.utoronto.ca

July 2013

Mark Lautens , O.C.

University Professor
J. Bryan Jones Distinguished Professor
AstraZeneca Professor of Organic Chemistry
NSERC/Merck-Frosst Industrial Research Chair

Department of Chemistry
Davenport Chemical Laboratories
80 St. George St.
University of Toronto
Toronto, Ontario
M5S 3H6

Tel: (416) 978-6083
Fax: (416) 946-8185
E-Mail: mlautens@chem.utoronto.ca

Curriculum Vitae

Personal
Place and Date of Birth	Hamilton, Ontario, Canada	July 9, 1959
Education
Harvard University	NSERC PDF with D. A. Evans	1985 - 1987
University of Wisconsin-Madison	Ph.D. with B. M. Trost	1985
University of Guelph	B.Sc. - Distinction	1981
Academic Positions
J. Bryan Jones Distinguished Professor	University of Toronto	2013 - 2018
University Professor	University of Toronto	2012 - present
NSERC/Merck Frosst Industrial Research Chair	NSERC/Merck Frosst	2003 - 2013
AstraZeneca Professor of Organic Synthesis	University of Toronto	1998 - present
Professor	University of Toronto	1995 - 1998
Associate Professor	University of Toronto	1992 - 1995
Assistant Professor	University of Toronto	1987 - 1992
Awards & Honors
University of Toronto Alumni Faculty Award	University of Toronto	2016
CIC Catalysis Award	CSC	2016
Officer of the Order of Canada	Governor General	2014
Killam Research Fellowship	Canada Council for the Arts	2013-2015
CIC Medal	Chemical Institute of Canada	2013
Fellow of the Royal Society of UK	Royal Society of Chemistry	2011
Pedler Award	Royal Society of Chemistry	2011
Senior Scientist Award	Alexander von Humboldt Foundation Berlin, Aachen and Gottingen	2009-2014
Visiting Professor	University of Berlin	2009
Visiting Professor	Université de Marseilles	2008
ICIQ Summer School	ICIQ Tarragona, Spain	2008
Attilio Corbella Summer School Professor	Italian Chemical Society	2007
Arthur C. Cope Scholar Award	American Chemical Society	2006
Alfred Bader Award	Canadian Society for Chemistry	2006
R. U. Lemieux Award	Canadian Society for Chemistry	2004
Solvias Prize	Solvias AG	2002
Fellow of the Royal Society of Canada	Royal Society of Canada	2001
Areas of Research Interest and Expertise
new synthetic methods metal catalyzed cycloaddition and annulation reactions asymmetric catalysis with focus on rhodium, nickel and palladium catalysts cyclopropane synthesis and reactions hydrometallation reactions reactions of organosilicon and organotin compounds fragmentation reactions new routes to medicinally/biologically interesting compounds heterocycle synthesis using metal catalysts

///////Multicomponent, Multicatalyst Reactions,  (MC)2R,  Dibenzazepine Synthesis, Mark Lautens, University of Toronto , Toronto, Ontario, Jennifer Tsoung

Asymmetric hydrogenation reaction of dehydro-α-amino acid (i.e., α-amino ester) over cinchonidine (CD) modified Pd catalyst has been studied by an array of in situ infrared spectroscopic methods, including transmission, diffuse reflectance (DR), and attenuated total reflectance (ATR). Transmission FTIR spectra probed the hydrogenation reaction process, revealed OH–O and NH–N hydrogen bonding interactions between the adsorbed CD and during the reaction. DR and ATR spectra of the hydrogenation reaction under different conditions, which are consistent with but slightly different from the transmission spectra, evidenced the successful hydrogenation of the compound. The incorporation of DR and microfluidics flow-through design allowed us to investigate the adsorption of CD on the Pd surface efficiently. The results revealed that the N-bonded CD on Pd surface in a tilted configuration had increased abundance on the Pd surface with high coverage. These valuable insights provided an image of the reaction pathway to the prochiral structure (precursor state).

Asymmetric Hydrogenation of α-Amino Ester Probed by FTIR Spectroscopy

Long Zhang†, Mehdi Lohrasbi‡, Uma Tumuluri‡, and Steven S. C. Chuang*†

† Department of Polymer Science, The University of Akron, Akron, Ohio 44325-3909, United States

‡ Department of Chemical and Biomolecular Engineering, The University of Akron, Akron, Ohio 44325-3906, United States

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.6b00222

*E-mail address: schuang@uakron.edu.

http://pubs.acs.org/doi/abs/10.1021/acs.oprd.6b00222

---

Catalytic asymmetric synthesis plays an important role in pharmaceutical and natural products synthesis. Homogeneous asymmetric catalysis has been well-developed over the past decades, while heterogeneous asymmetric catalysis has not undergone similar development due to the difficulty in investigating the interactions among the catalyst, the reactant, and the chiral modifier under reaction conditions. Heterogeneous catalysis exhibits unique features including (i) easiness of product/catalyst separation and catalyst regeneration, (ii) good chemical and physical stability, and (iii) feasibility in continuous processes.These features make it meaningful to investigate the molecular interactions and reactions on the surface of heterogeneous catalysts.

Fourier transform infrared (FTIR) spectroscopy is a versatile tool to provide insights into these interactions and reactions. There are three commonly used FTIR techniques—transmission, diffuse reflectance, and attenuated total reflectance (ATR). With proper design of in situ cells, these FTIR techniques can be used to probe the molecular interactions and reactions at the bulk and catalyst surface under reaction conditions.

Reaction Schematics and the Structure of Cinchonidine

Steven S. C. Chuang

Dr. Steven S.C. Chuang

Director, FirstEnergy Advanced Energy Research Center
Professor
Department of Polymer Science
Phone: 330-972-6993
Email: chuang@uakron.edu

---

Dr. Chuang's Research Website

http://schuang.uakron.edu

Education

• 1985 Ph.D., Chemical Engineering, University of Pittsburgh
• 1982 M.S., Chemical Engineering, New Jersey Institute of Technology
• 1977 Diploma, Chemical Engineering [5yr. program], National Taipei Inst. of Tech.

Contact Information

Dr. Steven S.C. Chuang
The University of Akron
Department of Polymer Science
Akron, Ohio 44325-3909

Email: chuang@uakron.edu
Voice: (330) 972-6993

Research Interests

• Professor Chuang investigates the structure of adsorbed species and its reactivity by transient infrared (IR) techniques. These techniques combined with traditional characterization methods such as XRD, UV-Vis, NMR, SEM, and TEM have been used for studying the nature of adsorbed species and reaction pathways during oxygenate synthesis, hydroformylation, partial oxidation, reduction of nitric oxide, nitric oxide decomposition, oxidative carbonylation, photocatalytic oxidation and reduction, carbon dioxide adsorption, reactions on solid oxide fuel cell catalysts, and synthesis organic/inorganic hybrid materials. The objectives of his research program are (i) developing an understanding of the reactivity of adsorbed species and its associated sites, (ii) using mechanism information to guide catalyst and sorbent preparation, and (iii) scaling up of catalytic and adsorption processes from laboratory scale to the pilot scale.

Faculty Profile [PDF]

http://www.uakron.edu/cpspe/documents/faculty-profiles/FacultyProfile-Chuang.pdf

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Real-time NMR spectroscopy has proven to be a rapid and an effective monitoring tool to study the hypervalent iodine(III) mediated cyclopropanation. With the ever increasing number of new synthetic methods for carbon–carbon bond formation, the NMR in situ monitoring of reactions is becoming a highly desirable enabling method. In this study, we have demonstrated the versatility of benchtop NMR using inline and online real-time monitoring methods to access mutually complementary information for process understanding, and we developed new approaches for real-time monitoring addressing challenges associated with better integration into continuous processes.

Continuous Processing and Efficient in Situ Reaction Monitoring of a Hypervalent Iodine(III) Mediated Cyclopropanation Using Benchtop NMR Spectroscopy

Batool Ahmed-Omer^*†, Eric Sliwinski^†, John P. Cerroti^‡, and Steven V. Ley^†

^† Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.

^‡Magritek GmbH, Gebäude VO (Building VO), Triwo Technopark Aachen, Philipsstrasse 8, 52068 Aachen, Germany

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.6b00177

 

*Email: batoolahmedomer@gmail.com.

http://pubs.acs.org/doi/full/10.1021/acs.oprd.6b00177

 

Steven V. Ley

Steven V. Ley received his PhD from Loughborough University in 1972, after which he carried out post-doctoral research with Professor Leo Paquette at Ohio State University, followed by Professor Derek Barton at Imperial College London. In 1975, he joined that Department as a lecturer and became Head of Department in 1989. In 1992, he moved to the 1702 BP Chair of Organic Chemistry at the University of Cambridge and became a Fellow of Trinity College. He was elected to the Royal Society in 1990 and was President of the Royal Society of Chemistry (RSC) 2000-02. Steve has been the recipient of many prizes and awards including the Yamada-Koga Prize, Nagoya Gold Medal, ACS Award for Creative Work in Synthetic Organic Chemistry and the Paul Karrer Medal.

 

  

Ethyl 2-(4-tert-butylphenyl)-1-nitrocyclopropanecarboxylate (5):

[E]-isomer: 1H NMR (600 MHz, CDCl3): δ 0.80-0.85 (t, J = 7.1 Hz, 3H), 1.29 (s, 9H), 2.16-2.21 (dd, J = 10.7, 6.6 Hz, 1H), 2.41-2.46 (dd, J = 9.1, 6.6 Hz, 1H), 3.72-3.77 (m, 1H), 3.88-4.04 (m, 2H), 7.12-7.15 (d, J = 8.3 Hz, 2H), 7.30-7.37 (d, J = 8.4 Hz, 2H).

13C NMR (150 MHz, CDCl3) δ 161.96, 151.38, 128.96, 128.15, 125.37, 71.71, 62.37, 34.54, 33.91, 31.21, 20.73, 13.35.

HRMS (ESI) Calcd. for C16H21NO4 ([M+H]+): 292.15, Found 292.15:

[Z]-isomer: 1H NMR (600 MHz, CDCl3): δ 1.30 (s, 9H), 1.34-1.37 (t, J = 7.1 Hz, 3H), 2.00-2.04 (dd, J = 9.9, 6.9 Hz, 1H), 2.64-2.68 (dd, J = 9.2, 6.9 Hz, 1H), 3.43-3.48 (t, J = 9.6 Hz, 1H), 4.31-4.41 (m, 2H), 7.14-7.17 (d, J = 8.3 Hz, 2H), 7.32-7.36 (d, J = 8.4 Hz, 2H).

13C NMR (150 MHz, CDCl3) δ 165.40, 151.56, 128.33, 127.99, 125.63, 72.63, 63.14, 34.55, 33.48, 31.22, 20.08, 13.98.

Zhu, S.; Perman, J. A.; Zhang, X. P. Angew. Chem. Int. Ed. 2008, 47, 8460-8463.

Professor Steven V. Ley CBE FRS

ORGANIC CHEMISTRY RESEARCH GROUP

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Blooms of the microalga Prymnesium parvum cause devastating fish kills worldwide, which are suspected to be caused by the supersized ladder-frame polyether toxins prymnesin-1 and -2. These toxins have, however, only been detected from P. parvum in rare cases since they were originally described two decades ago. Here, we report the isolation and characterization of a novel B-type prymnesin, based on extensive analysis of 2D- and 3D-NMR data of natural as well as 90% 13C enriched material. B-type prymnesins lack a complete 1,6-dioxadecalin core unit, which is replaced by a short acyclic C2 linkage compared to the structure of the original prymnesins. Comparison of the bioactivity of prymnesin-2 with prymnesin-B1 in an RTgill-W1 cell line assay identified both compounds as toxic in the low nanomolar range. Chemical investigations by liquid chromatography high-resolution mass spectrometry (LC-HRMS) of 10 strains of P. parvum collected worldwide showed that only one strain produced the original prymnesin-1 and -2, whereas four strains produced the novel B-type prymnesin. In total 13 further prymnesin analogues differing in their core backbone and chlorination and glycosylation patterns could be tentatively detected by LC-MS/HRMS, including a likely C-type prymnesin in five strains. Altogether, our work indicates that evolution of prymnesins has yielded a diverse family of fish-killing toxins that occurs around the globe and has significant ecological and economic impact.

Chemodiversity of Ladder-Frame Prymnesin Polyethers in Prymnesium parvum

Silas Anselm Rasmussen†, Sebastian Meier‡, Nikolaj Gedsted Andersen§, Hannah Eva Blossom§, Jens Øllgaard Duus‡, Kristian Fog Nielsen†, Per Juel Hansen*§, and Thomas Ostenfeld Larsen*†

† Department of Biotechnology and Biomedicine, Technical University of Denmark, Søltofts Plads 221, 2800 Kgs. Lyngby,Denmark

‡ Department of Chemistry, Technical University of Denmark, Kemitorvet 207, 2800 Kgs. Lyngby, Denmark

§ Marine Biological Section, Department of Biology, Copenhagen University, Strandpromenaden 5, 2100 Helsingør,Denmark

J. Nat. Prod., Article ASAP

DOI: 10.1021/acs.jnatprod.6b00345

Publication Date (Web): August 23, 2016

Copyright © 2016 The American Chemical Society and American Society of Pharmacognosy

*Tel (P. J. Hansen): (+45) 35321985. E-mail: pjhansen@bio.ku.dk., *Tel (T. O. Larsen): (+45) 45252632. E-mail: tol@bio.dtu.dk.

http://pubs.acs.org/doi/full/10.1021/acs.jnatprod.6b00345

 

Figure 1. LC-MS/HRMS screening of 10 P. parvum strains. (A) Summed EICs (doubly charged) of all prymnesin-like molecules in 10 worldwide-distributed strains of P. parvum. Green EIC was created for original prymnesin-1 and -2. Red EICs show B-type prymnesins. Blue EICs show tentatively identified C-type prymnesins. (B) MS/HRMS spectra of [M + 2H]2+: (top) prymnesin-1 and -2, (middle) prymnesin-B1 and -B2, (bottom) tentatively assigned C-type prymnesins. Δ66 shows a loss of a pentose (m/z 66.021, doubly charged) and Δ81 a loss of a hexose (m/z 81.026, doubly charged). Asterisk (*) denotes tentatively characterized by MS/MS, UV, and chiral-phase GC-MS.

aChemical shifts are reported in CD3OD and referenced to δH 3.31 ppm and δC 47.9 ppm at 313 K. n.d. = not detected.

 

////////////Chemodiversity, Ladder-Frame, Prymnesin Polyethers, Prymnesium parvum

aChemical shifts are reported in CD3OD and referenced to δH 3.31 ppm and δC 47.9 ppm at 313 K. n.d. = not detected.

 

////////////Chemodiversity, Ladder-Frame, Prymnesin Polyethers, Prymnesium parvum

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